High refractive index aromatic-based siloxane difunctional macromonomers

ABSTRACT

Optically transparent, relatively high refractive index polymeric compositions and ophthalmic devices such as intraocular lenses, corneal inlays and contact lenses made therefrom are described herein. The preferred polymeric compositions are produced through the polymerization of one or more aromatic-based siloxane macromonomers or the copolymerization of one or more aromatic-based siloxane macromonomers with one or more non-siloxy aromatic-based monomers, non-aromatic-based hydrophobic monomers or non-aromatic-based hydrophilic monomers.

FIELD OF THE INVENTION

[0001] The present invention relates to macromonomers useful in themanufacture of biocompatible medical devices. More particularly, thepresent invention relates to aromatic-based siloxane difunctionalmacromonomers capable of polymerization alone or copolymerization withother monomers. Upon polymerization or copolymerization, the subjectmacromonomers form polymeric compositions having desirable physicalcharacteristics and refractive indices useful in the manufacture ofophthalmic devices.

BACKGROUND OF THE INVENTION

[0002] Since the 1940's ophthalmic devices in the form of intraocularlens (IOL) implants have been utilized as replacements for diseased ordamaged natural ocular lenses. In most cases, an intraocular lens isimplanted within an eye at the time of surgically removing the diseasedor damaged natural lens, such as for example, in the case of cataracts.For decades, the preferred material for fabricating such intraocularlens implants was poly(methyl methacrylate), which is a rigid, glassypolymer.

[0003] Softer, more flexible IOL implants have gained in popularity inmore recent years due to their ability to be compressed, folded, rolledor otherwise deformed. Such softer IOL implants may be deformed prior toinsertion thereof through an incision in the cornea of an eye. Followinginsertion of the IOL in an eye, the IOL returns to its originalpre-deformed shape due to the memory characteristics of the softmaterial. Softer, more flexible IOL implants as just described may beimplanted into an eye through an incision that is much smaller, i.e.,less than 4.0 mm, than that necessary for more rigid IOLs, i.e., 5.5 to7.0 mm. A larger incision is necessary for more rigid IOL implantsbecause the lens must be inserted through an incision in the corneaslightly larger than the diameter of the inflexible IOL optic portion.Accordingly, more rigid IOL implants have become less popular in themarket since larger incisions have been found to be associated with anincreased incidence of postoperative complications, such as inducedastigmatism.

[0004] With recent advances in small-incision cataract surgery,increased emphasis has been placed on developing soft, foldablematerials suitable for use in artificial IOL implants. In general, thematerials of current commercial IOLs fall into one of three generalcategories: silicones, hydrophilic acrylics and hydrophobic acrylics.

[0005] In general, high water content hydrophilic acrylics or“hydrogels” have relatively low refractive indices, making them lessdesirable than other materials with respect to minimal incision size.Low refractive index materials require a thicker IOL optic portion toachieve a given refractive power. Silicone materials may have a higherrefractive index than high-water content hydrogels, but tend to unfoldexplosively after being placed in the eye in a folded position.Explosive unfolding can potentially damage the corneal endotheliumand/or rupture the natural lens capsule and associated zonules. Lowglass transition temperature hydrophobic acrylic materials are desirablebecause they typically have a high refractive index and unfold moreslowly and more controllably than silicone materials. Unfortunately, lowglass transition temperature hydrophobic acrylic materials, whichcontain little or no water initially, may absorb pockets of water invivo causing light reflections or “glistenings.” Furthermore, it may bedifficult to achieve ideal folding and unfolding characteristics due tothe temperature sensitivity of some acrylic polymers.

[0006] Because of the noted shortcomings of current polymeric materialsavailable for use in the manufacture of ophthalmic implants, there is aneed for stable, biocompatible polymeric materials having desirablephysical characteristics and refractive index.

SUMMARY OF THE INVENTION

[0007] Soft, foldable, high refractive index, high elongation polymericcompositions of the present invention are produced through thepolymerization of aromatic-based siloxane macromonomers, either alone orwith other monomers. The subject macromonomers are synthesized through atwo-phase reaction scheme. The polymeric compositions produced from thesiloxane macromonomers so synthesized have ideal physical properties forthe manufacture of ophthalmic devices. The polymeric compositions of thepresent invention are transparent, of relatively high strength fordurability during surgical manipulations, of relatively high elongation,of relatively high refractive index and are biocompatible. The subjectpolymeric compositions are particularly well suited for use asintraocular lens (IOL) implants, contact lenses, keratoprostheses,corneal rings, corneal inlays and the like.

[0008] Preferred aromatic-based siloxane macromonomers for use inpreparing the polymeric compositions of present invention have thegeneralized structures represented by Formula 1 and Formula 2 below,

[0009] wherein the R groups may be the same or different aromatic-basedsubstituents; R₁ is an aromatic-based substituent or an alkyl; x is anon-negative integer; and y is a natural number.

[0010] Accordingly, it is an object of the present invention to providetransparent, polymeric compositions having desirable physicalcharacteristics for the manufacture of ophthalmic devices.

[0011] Another object of the present invention is to provide polymericcompositions of relatively high refractive index.

[0012] Another object of the present invention is to provide polymericcompositions suitable for use in the manufacture of intraocular lensimplants.

[0013] Another object of the present invention is to provide polymericcompositions that are biocompatible.

[0014] Still another object of the present invention is to providepolymeric compositions that are economical to produce.

[0015] These and other objectives and advantages of the presentinvention, some of which are specifically described and others that arenot, will become apparent from the detailed description and claims thatfollow.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention relates to novel aromatic-based siloxanemacromonomers synthesized through a two-phase reaction scheme. Thesubject aromatic-based siloxane macromonomers are useful in theproduction of biocompatible polymeric compositions. The subjectpolymeric compositions have particularly desirable physical properties.The subject polymeric compositions have a relatively high refractiveindex of approximately 1.45 or greater and a relatively high elongationof approximately 100 percent or greater. Accordingly, the subjectpolymeric compositions are ideal for use in the manufacture ofophthalmic devices. The aromatic-based siloxane macromonomers of thepresent invention are generally represented by the structures of Formula1 and Formula 2 below:

[0017] wherein the R groups may be the same or different C₆₋₃₀aromatic-based substituents such as for example but not limited to

[0018] ; R₁ is a C₆₋₃₀ aromatic-based substituent as defined for R or aC₁₋₄ alkyl such as for example but not limited to methyl or propyl; x isa non-negative integer; and y is a natural number.

[0019] The aromatic-based siloxane macromonomers of the presentinvention may be synthesized through a two-phase reaction scheme. Thefirst phase of the two-phase reaction scheme is a co-ring openingpolymerization of a hydride functionalized cyclic siloxane with amethacrylate-capped disiloxane. The resultant siliconehydride-containing macromonorner is placed under high vacuum with heatto remove the unreacted silicone hydride cyclics. The second phase ofthe two-phase reaction scheme consists of a platinum-catalyzedhydrosilylation of an allylic functionalized aromatic with the hydridecontaining siloxane. The reaction is monitored for loss of hydride byboth infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy.NMR analysis of the final product confirms the molecular structure. Inproducing the subject macromonomers, a thirty percent excess of thestarting allylic aromatic was used and no attempt was made to remove thesame following completion of the hydrosilylation. Synthesis of thesubject aromatic-based siloxane macromonomers is described is stillgreater detail in the examples set forth below. Additionally, specificexamples of aromatic-based siloxane macromonomers of the presentinvention prepared in accordance with the above-described two-phasereaction scheme are set forth below in Table 1. TABLE 1 Side Chain (R)Structure Si/O Mole % R.I. pentafluorophenylpropyl

18/7 1.44 phenylpropyl

18/7 1.46 p-methoxyphenylpropyl p-methoxyphenylpropylp-methoxyphenylpropyl p-methoxyphenylpropyl

18/7 13/13 7/18 13/37 1.48 1.50 1.52 1.52 3,4-dimethoxyphenylpropyl

18/7 1.48 2-naphthylpropyl ether 2-naphthylpropyl ether 2-naphthylpropylether

18/7 13/13 13/37 1.53 1.55 1.57 diphenyldipropylether

13/13 1.53 triphenylsilylpropyl

13/13 1.58

[0020] The aromatic-based siloxane macromonomers of the presentinvention may be polymerized alone or as a copolymer with one or morearomatic non-siloxy based monomers, non-aromatic-based hydrophilicmonomers, non-aromatic-based hydrophobic monomers or a combinationthereof, to produce polymeric compositions of the present invention.

[0021] Examples of non-siloxy aromatic-based monomers useful forcopolymerization with one or more aromatic-based siloxane macromonomersof the present invention include for example but are not limited to2-phenyoxyethyl methacrylate, 3,3-diphenylpropyl methacrylate,2-(1-naphthylethyl methacrylate) and 2-(2-naphthylethyl methacrylate)but preferably 2-(1-naphthylethyl methacrylate) for increased refractiveindex.

[0022] Examples of non-aromatic-based hydrophilic monomers useful forcopolymerization with one or more aromatic-based siloxane macromonomersof the present invention include for example but are not limited toN,N-dimethylacrylamide and methyl methacrylate, but preferablyN,N-dimethylacrylamide for increased hydrophilicity.

[0023] The physical and mechanical properties of copolymers producedfrom naphthyl side-chain siloxane macromonomers [Si(NEM)] withnaphthylethyl methacrylate (NEM) and N,N-dimethylacrylamide (DMA) areset forth below in Table 2. TABLE 2 Mod. Tear Composition R.I. (g/mm²)(g/mm) Rec. % H₂O [Si(NEM)]/NEM/DMA 100/0/0 1.550 129 2 93 0 80/20/01.563 222 27 80 0 80/20/5 74 1.4 80/20/10 1.556 724 55 64 2.7 80/20/201.536 357 31 77 6.5 85/15/0 1.556 103 14 87 0 85/15/10 1.553 332 32 701.7 85/15/20 1.533 289 18 81 8.4 Commercial 1.43 300 50 81 0 siliconeelastomer

[0024] R.I.=refractive index

[0025] Mod.=modulus

[0026] Rec.=recovery, which is a measure of the ability of a material torecover to its original shape when stretched and is measured as thepercentage of recovery.

[0027] Examples of non-aromatic-based hydrophobic monomers useful forcopolymerization with one or more aromatic-based siloxane macromonomersof the present invention include for example but are not limited to2-ethylhexyl methacrylate, 3-methacryloyloxypropyldiphenylmethylsilaneand 2-phenyoxyethyl methacrylate but preferably3-methacryloyloxypropyldiphenylmethylsilane for increased refractiveindex. The physical and mechanical properties of copolymers producedfrom naphthyl side-chain siloxane macromonomers [Si(NEM)] with3-methacryloyloxypropyidiphenylmethylsilane (MDPPM) and DMA are setforth below in Table 3. TABLE 3 Mod. Tear Composition R.I. (g/mm²)(g/mm) Rec. % H₂O [SI(NEM)]/MDPPM/DMA 100/0/0 1.550 129 2 93 0 80/20/01.556 145 8 95 0 75/25/0 1.556 144 12 90 0 70/30/0 1.560 138 17 88 070/30/10 1.554 227 31 69 2.9 70/30/20 1.540 257 44 79 7.5 Commercial1.43 300 50 81 0 silicone elastomer

[0028] R.I.=refractive index

[0029] Mod.=modulus

[0030] Rec.=recovery, which is a measure of the ability of a material torecover to its original shape when stretched and is measured as thepercentage of recovery.

[0031] No water, low water having less than 15 percent water contentweight/volume (W/V) and high water “hydrogels” having 15 percent orhigher water content W/V polymeric compositions of the present inventionhaving ideal physical characteristics for ophthalmic device manufactureare described herein. Although the monofunctional siloxane macromonomersof Formula 2 polymerize or copolymerize to form crosslinkedthree-dimensional networks, one or more crosslinking agents may be addedin quantities of preferably less than 10 percent W/V prior topolymerization or copolymerization.

[0032] Examples of suitable crosslinking agents include but are notlimited to diacrylates and dimethacrylates of triethylene glycol, butylglycol, hexane-1,6-diol, thio-diethylene glycol, ethylene glycol andneopentyl glycol, N,N′-dihydroxyethylene bisacrylamide, diallylphthalate, triallyl cyanurate, divinylbenzene, ethylene glycol divinylether, N,N′-methylene-bis-(meth)acrylamide, sulfonated divinylbenzeneand divinylsulfone.

[0033] In order to produce polymeric compositions of the presentinvention from the subject monofunctional siloxane macromonomers ofFormula 2, one or more strengthening agents must be used. However,strengthening agents are not necessary to produce polymeric compositionsof the present invention from the subject difunctional siloxanemacromonomers of Formula 1. One or more strengthening agents arepreferably added in amounts less than approximately 50 percent W/V, butmore preferably in amounts less than 25 percent W/V, to themacromonomers of Formula 2 prior to polymerization or copolymerizationthereof.

[0034] Examples of suitable strengthening agents are described in U.S.Pat. Nos. 4,327,203, 4,355,147 and 5,270,418, each incorporated hereinin its entirety by reference. Specific examples, not intended to belimiting, of such strengthening agents include cycloalkyl acrylates andmethacrylates, such as for example tert-butylcyclohexyl methacrylate andisopropylcyclopentyl acrylate.

[0035] One or more suitable ultraviolet light absorbers may optionallybe used in quantities typically less than 2 percent W/V in themanufacture of the subject polymeric compositions. Examples of suchultraviolet light absorbers include for example but are not limited toβ-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate,4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone,4-methacryloyloxy-2-hydroxybenzophenone,2-(2′-methacryloyloxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole,2-[3′-tert-butyl-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole,2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazoleand2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-chlorobenzotriazolewherein β-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is thepreferred ultraviolet light absorber.

[0036] The subject siloxane macromonomers and polymeric compositionsmanufactured therefrom are described in still greater detail in theexamples that follow.

EXAMPLE 1 Synthesis of Macromonomer (Two-part Synthetic Scheme)

[0037] Part A: Methacrylate End-capped Hydride FunctionalizedMacromonomer Synthesis

[0038] To a 1000 ml round bottom flask under dry nitrogen was added D₄(octamethylcyclotetrasiloxane), D₄H (tetramethylcyclotetrasiloxane) andM₂ (1,3-bis(4-methacryloyloxybutyl)tetramethyidisiloxane (molar ratio ofeach component dependent on desired chain length and mole % hydridesubstitution). Trifluoromethanesulfonic acid (0.25%) was added asinitiator. The reaction mixture was stirred 24 hours with vigorousstirring at room temperature. Sodium bicarbonate was then added and thereaction mixture was again stirred for 24 hours. The resultant solutionwas filtered through a 0.3 μTeflon® (E. I. du Pont de Nemours andCompany, Wilmington, Del.) filter. The filtered solution was vacuumstripped and placed under vacuum (>0.1 mm Hg) at 50° C. to remove theunreacted silicone cyclics. The resulting silicone hydridefunctionalized siloxane was a viscous, clear fluid.

[0039] Part B: General Procedure for the Synthesis of the MethacrylateEnd-capped Aromatic Side-chain Siloxanes

[0040] To a 500 mL round bottom flask equipped with a magnetic stirrerand water condenser was added the methacrylate end-capped macromonomer(prepared in Part A above), the aromatic functionalized allylic ether,tetramethyldisiloxane platinum complex (2.5 mL of a 10% solution inxylenes), 75 mL of dioxane and 150 mL of anhydrous tetrahydrofuran undera nitrogen blanket. The reaction mixture was heated to 75° C. and thereaction was monitored by IR and ¹H-NMR spectroscopy for loss ofsilicone hydride. The reaction was complete in 4 to 5 hours of reflux.The resulting solution was placed on a rotoevaporator to removetetrahydrofuran and dioxane. The resultant crude product was dilutedwith 300 mL of a 20% methylene chloride in pentane solution and passedthrough a 15 gram column of silica gel using a 50% solution of methylenechloride in pentane as eluant. The collected solution was again placedon the rotoevaporator to remove solvent and the resultant clear oil wasplaced under vacuum (>0.1 mm Hg) at 50° C. for four hours. The resultingaromatic side-chain siloxane was a viscous, clear fluid.

EXAMPLE 2

[0041] To 80 parts of a 13/13 [Si(NEM)] macromonomer was added 20 partsof naphthylethyl methacrylate and 0.5% of Irgacure™ 819 (Ciba-Geigy,Basel, Switzerland) as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chemical Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in isopropanol (IPA) for four hours, followed byair-drying and a 30 mm vacuum to remove the IPA. The clear tack-freefilms possessed a modulus of 222 g/mm², tear strength of 29 g/mm,recovery of 80% and a refractive index of 1.563. Commercial gradesilicone rubber exhibits a modulus of 300 g/mm², a tear of 50 g/mm,recovery of 81% and a refractive index of only 1.43.

EXAMPLE 3

[0042] To 80 parts of a 13/13 [Si(NEM)] macromonomer was added 20 partsof methyl methacrylate and 0.5% of Irgacure™ 819 as the UVphotoinitiator and 0.25% of a commercial triazole UV blocker (AldrichChemical Co). The clear solution was sandwiched between two silanizedglass plates using metal gaskets and exposed to UV radiation for twohours. The resultant films were released and extracted in IPA for fourhours, followed by air-drying and a 30 mm vacuum to remove the IPA. Theclear tack-free films possessed a modulus of 1123 g/mm², a tear strengthof 93 g/mm, recovery of 60% and a refractive index of 1.538.

EXAMPLE 4

[0043] To 80 parts of a 13/13 [Si(NEM)] macromonomer was added 20 partsof naphthylethyl methacrylate, 20 parts of N,N-dimethylacrylamide and0.5% of Irgacure™ 819 as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chemical Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in IPA for four hours, followed by air-drying and a 30 mmvacuum to remove the IPA. The resultant film was hydrated at roomtemperature overnight in borate buffered saline. The clear tack-freefilms possessed a modulus of 357 g/mm², a tear strength of 31 g/mm,recovery of 77%, a water content of 6.5% and a refractive index of1.536.

EXAMPLE 5

[0044] To 80 parts of a 13/13 [Si(NEM)] macromonomer was added 30 partsof 3-methacryloyloxypropylmethyldiphenylsilane, 20 parts ofN,N-dimethylacrylamide and 0.5% of Irgacure™ 819 as the UVphotoinitiator and 0.25% of a commercial triazole UV blocker (AldrichChemical Co). The clear solution was sandwiched between two silanizedglass plates using metal gaskets and exposed to UV radiation for twohours. The resultant films were released and extracted in IPA for fourhours, followed by air-drying and a 30 mm vacuum to remove the IPA. Theresultant film was hydrated at room temperature overnight in boratebuffered saline. The clear tack-free films possessed a modulus of 257g/mm², a tear strength of 44 g/mm, recovery of 79%, a water content of7.5% and a refractive index of 1.54.

[0045] The polymeric compositions of the present invention are ofrelatively high refractive index, relatively high elongation andrelatively high clarity. The polymeric compositions of the presentinvention with the desirable physical properties noted above areparticularly useful in the manufacture of ophthalmic devices such as butnot limited to relatively thin, foldable intraocular lens (IOL) implantsand corneal inlays.

[0046] IOLs having relatively thin optic portions are critical inenabling a surgeon to minimize surgical incision size. Keeping thesurgical incision size to a minimum reduces intraoperative trauma andpostoperative complications. A relatively thin IOL optic portion is alsocritical for accommodating certain anatomical locations in the eye suchas the anterior chamber and the ciliary sulcus. IOLs may be placed inthe anterior chamber for increasing visual acuity in either aphakic orphakic eyes, or placed in the ciliary sulcus for increasing visualacuity in phakic eyes.

[0047] The high refractive index polymeric compositions of the presentinvention have the flexibility required to allow implants manufacturedfrom the same to be folded or deformed for insertion into an eye throughthe smallest possible surgical incision, i.e., 3.5 mm or smaller. It isunexpected that the subject polymeric compositions could possess theideal physical properties described herein. The ideal physicalproperties of the subject polymeric compositions are unexpected sincehigh refractive index monomers typically lend to polymers that haveincreased crystallinity and decreased clarity, which does not hold truein the case of the subject polymeric compositions.

[0048] Ophthalmic devices such as but not limited to IOLs manufacturedusing the polymeric compositions of the present invention can be of anydesign capable of being rolled or folded for implantation through arelatively small surgical incision, i.e., 3.5 mm or less. For example,ophthalmic devices such as IOLs typically comprise an optic portion andone or more haptic portions. The optic portion reflects light onto theretina and the permanently attached haptic portions hold the opticportion in proper alignment within an eye. The haptic portions may beintegrally formed with the optic portion in a one-piece design orattached by staking, adhesives or other methods known to those skilledin the art in a multipiece design.

[0049] The subject ophthalmic devices, such as for example IOLs, may bemanufactured to have an optic portion and haptic portions made of thesame or differing materials. Preferably, in accordance with the presentinvention, both the optic portion and the haptic portions of the IOLsare made of polymeric compositions of the present invention.Alternatively however, the IOL optic portion and haptic portions may bemanufactured from one or more differing materials and/or one or morediffering formulations of the polymeric compositions of the presentinvention, such as described in U.S. Pat. Nos. 5, 217,491 and 5,326,506,each incorporated herein in its entirety by reference.

[0050] The siloxane macromonomers of the present invention may bereadily cured in cast shapes, as discussed in more detail below, by oneor more conventional methods. Such methods include for example but arenot limited to ultraviolet light polymerization, visible lightpolymerization, microwave polymerization, thermal polymerization, freeradical thermal polymerization or combinations thereof.

[0051] Suitable free radical thermal polymerization initiators which maybe added to the monomers of the present invention include for examplebut are not limited to organic peroxides, such as acetyl peroxide,lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoylperoxide, tert-butyl peroxypivalate, peroxydicarbonate and the like.Preferably such an initiator is employed in a concentration ofapproximately 0.01 to 1 percent by weight of the total monomer mixture.Representative UV initiators include those known in the field such asfor example but not limited to benzoin methyl ether, benzoin ethylether, Darocur™ 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries),Irgacur™ 651 and 184 (Ciba-Geigy, Basel, Switzerland).

[0052] Once the particular material or materials are selected for theparticular ophthalmic device of choice, the same is either cast in moldsof the desired shape or cast in the form of rods and lathed or machinedinto disks. If cast in the form of rods and lathed or machined intodisks, the disks are lathed or machined into IOLs, corneal rings or thelike at low temperatures below the glass transition temperature(s) ofthe material(s). The ophthalmic devices, whether molded orlathed/machined, are then cleaned, polished, packaged and sterilized bymethods known to those skilled in the art.

[0053] In addition to intraocular lenses, the polymeric compositions ofthe present invention are also suitable for use in the manufacture ofother ophthalmic devices such as contact lenses, keratoprostheses,capsular bag extension rings, corneal inlays, corneal rings or likedevices.

[0054] IOLs manufactured using the unique polymeric compositions of thepresent invention are used as customary in the field of ophthalmology.For example, in a surgical procedure, an incision is placed in thecornea of an eye. Most commonly through the corneal incision the naturallens of the eye is removed (aphakic application) such as in the case ofa cataractous natural lens. An IOL is then inserted into the anteriorchamber, posterior chamber or lens capsule of the eye prior to closingthe incision. However, the subject ophthalmic devices may be used inaccordance with other surgical procedures known to those skilled in thefield of ophthalmology.

[0055] While there is shown and described herein macromonomers,polymeric compositions, methods of producing the macromonomers andpolymeric compositions, methods of producing ophthalmic devices usingthe polymeric compositions and methods of using ophthalmic devicesmanufactured from the polymeric compositions, all in accordance with thepresent invention, it will be manifest to those skilled in the art thatvarious modifications may be made without departing from the spirit andscope of the underlying inventive concept. The present invention islikewise not intended to be limited to particular structures hereinshown and described except insofar as indicated by the scope of theappended claims.

We claim:
 1. Aromatic-based siloxane macromonomers comprising:

wherein the R groups may be the same or different aromatic-basedsubstituents; R₁ is an aromatic-based substituent or an alkyl; x is anon-negative integer; and y is a natural number.
 2. The macromonomer ofclaim 1 wherein said R groups may be the same or different C₆₋₃₀aromatic-based substituents.
 3. The macromonomer of claim 1 wherein saidR groups may be the same or different aromatic-based substituentsselected from the group consisting of


4. The macromonomer of claim 1 wherein said R₁ groups may be the same ordifferent aromatic-based substituents or alkyl substituents.
 5. Themacromonomer of claim 1 wherein said R₁ groups may be the same ordifferent C₆₋₃₀ aromatic-based substituents or C₁₋₄ alkyl substituents.6. A polymeric composition produced through the polymerization of one ormore macromonomers of claim
 1. 7. A polymeric composition producedthrough the copolymerization of one or more macromonomers of claim 1with one or more non-siloxy aromatic-based monomers.
 8. A polymericcomposition produced through the copolymerization of one or moremacromonomers of claim 1 with one or more non-aromatic-based hydrophobicmonomers.
 9. A polymeric composition produced through thecopolymerization of one or more macromonomers of claim 1 with one ormore non-aromatic-based hydrophilic monomers.
 10. A method of producingthe aromatic-based siloxane macromonomers of claim 1 comprising:polymerizing a hydride functionalized cyclic siloxane with amethacrylate-capped disiloxane to form a hydride containing siloxane;and hydrosilylizing with a catalyst and an allylic functionalizedaromatic, said hydride containing siloxane.
 11. The polymericcompositions of claim 7 wherein said one or more non-siloxyaromatic-based monomers are selected from the group consisting of2-phenyloxyethyl methacrylate, 3,3-diphenylpropyl methacrylate,2-(1-naphthylethyl methacrylate) and 2-(2-naphthylethyl methacrylate).12. The polymeric compositions of claim 8 wherein said one or morenon-aromatic-based hydrophobic monomers are selected from the groupconsisting of 2-ethylhexyl methacrylate,3-methacryloyloxypropyldiphenylmethylsilane and 2-phenyoxyethylmethacrylate.
 13. The polymeric compositions of claim 9 wherein said oneor more non-aromatic-based hydrophilic monomers are selected from thegroup consisting of N,N-dimethylacrylamide and methyl methacrylate. 14.A method of producing ophthalmic devices from the polymeric compositionsof claim 6, 7, 8 or 9 comprising: casting one or more polymericcompositions in the form of a rod; lathing or machining said rod intodisks; and lathing or machining said disks into ophthalmic devices. 15.A method of producing ophthalmic devices from the polymeric compositionsof claim 6, 7, 8 or 9 comprising: pouring one or more polymericcompositions into a mold prior to curing; curing said one or morepolymeric compositions; and removing said one or more polymericcompositions from said mold following curing thereof.
 16. A method ofusing the ophthalmic device of claim 14 or 15 comprising: making anincision in the cornea of an eye; and implanting said ophthalmic devicewithin the eye.
 17. The method of claim 14, 15 or 16 wherein saidophthalmic device is an intraocular lens or corneal inlay.
 18. Themethod of claim 14 or 15 wherein said ophthalmic device is a contactlens.
 19. The polymeric composition of claim 6, 7, 8 or 9 wherein one ormore strengthening agents are added prior to polymerization orcopolymerization selected from the group consisting of cycloalkylacrylates and methacrylates.
 20. The polymeric composition of claim 6,7, 8 or 9 wherein one or more crosslinking agents are added prior topolymerization or copolymerization selected from the group consisting ofdiacrylates and dimethacrylates of triethylene glycol, butyl glycol,hexane-1,6-diol, thio-diethylene glycol, ethylene glycol and neopentylglycol, N,N′-dihydroxyethylene bisacrylamide, diallyl phthalate,triallyl cyanurate, divinylbenzene, ethylene glycol divinyl ether,N,N′-methylene-bis-(meth)acrylamide, sulfonated divinylbenzene anddivinylsulfone.